ALCOHOLS

Alcohols (or alkanols) are aliphatic organic compounds containing the –OH group as the functional
group.
Classification of alcohols
Alcohols are classified as primary (1o), secondary (2o) or tertiary (3o), depending on the number of alkyl
groups bonded to the hydroxyl-bearing carbon.

Naming of alcohols
1. Simple alcohols are named by the IUPAC system as derivatives of the parent alkane, using the
suffix –ol.
2. Select the longest carbon chain containing the hydroxyl group, and derive the parent name by
replacing the –e ending of the corresponding alkane with –ol.
3. Number the alkane chain (carbons) by beginning at the end nearer the hydroxyl group.
4. Number the substituents according to their position on the chain, and write the name listing the
substituents in alphabetical order.
Practice questions
1. Draw the structures of the following compounds
a. 2-methyl-2-pentanol (2-methylpentan-2-ol)
b. 2,3-Dimethyl-1-butanol
c. 1-methylcyclohexanol
d. Cis-cyclohexan-1,2-diol (Cis-1,2-cyclohexanediol)
e. 2-propen-1-ol
f. 2-methyl-2-propanol
g. 1,2-ethanediol
h. Propan-1,2,3-triol (glycerol)
i. 3-phenyl-2-butanol
Properties of alcohols
 Alcohols are of the form R-OH. R, the alkyl group, is non-polar while the -OH is polar. The -OH
gives the alcohols their characteristic physical properties. Depending on its size and shape, the
alkyl group modifies these properties.
Boiling points
 They have high boiling points compared to the hydrocarbons having the same number of carbon
atoms/same molecular weight. It increases with increase in molecular weight (no. of carbon
atoms) and decrease with branching, which causes steric hindrance. The BP are exceptionally
higher compared to the corresponding hydrocarbons because they are polar and form hydrogen
bonds in the liquid state i.e. through their hydroxyl group the alcohol molecules are capable of
hydrogen bonding. This comes about because the hydroxyl group is polar as it contains hydrogen
bonded to the highly electronegative element, oxygen.

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 A positively polarized –OH hydrogen atom from one molecule is attracted to a lone pair
of electrons on a negatively polarized oxygen atom of another molecule, resulting in a
weak force that holds the molecules together. These intermolecular attractions must be
overcome for the molecules to break free from the liquid and enter the vapor state, so the
boiling point is raised.

Hydrogen bonds hold molecules together tightly and therefore to break them a lot of energy is
needed, hence high BP temperatures.
Solubility in water
 Alcohols dissolve in water just as they do to each other—through hydrogen bonding. Solubility in
water decreases with increase in chain. Why? As the alkane-like alkyl group becomes larger
(longer), water solubility decreases. The borderline between solubility and insolubility in water
occurs at about 4-5 carbon atoms for normal primary alcohols. As the homologous series of
alcohols is ascended, the influence of the OH- group becomes less and less compared with that of
the increasing large hydrocarbon portion. The properties of the longer chain alcohols, therefore,
are more and more towards those of the corresponding alkanes.
 They dissolve in other polar molecules because they are also polar—like dissolves like.

Preparation of alcohols
1. Hydrolysis of alkyl halides using a dilute base.

R—X + OH- (NaOH or KOH) → ROH + X- (or HX)

e.g.

2. Hydration of alkenes
Reaction of an alkene with water
CH2=CH2 + H2O → CH2OHCH3
3. Synthesis of diols from alkenes
Reaction of alkenes with alkaline KMnO4

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 4. Reaction of Carbonyl compounds with Grignard Reagents
Grignard reagents (RMgX) are prepared by the reaction of alkyl halides with Mg in ether or THF
solution.
R-X + Mg → R-MgX X= Cl, Br, or I
Grignard reagent

Many alcohols are obtained from Grignard reactions, depending on the reactants. They react:
 With formaldehyde (H2C=O) to give primary alcohols.
 With aldehydes to give secondary alcohols.
 With ketones to give tertiary alcohols.
 Mechanism:

Preparation of alcohols by rxn of Esters with Grignard Reagents

Esters react with Grignard reagents to give tertiary alcohols in which two of the substituents bonded to the
hydroxyl-bearing carbon have come from the Grignard Reagent (just as LiAlH4 adds two hydrogens).
Practice Questions
1. Give the structure and names of the products of the following.

2. Show the products obtained from the addition of methylmagnesium bromide to the following
compounds:

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 (a) Cyclopentanone
(b) Diphenyl Ketone
(c) 3-Hexanone
3. Use a Grignard reaction to prepare the following alcohols
a. 2-methyl-2-propanol
b. 1-methylcyclohexanol
c. 3-methyl-3-pentanol
d. 2-phenyl-2-butanol

5. Reduction of aldehydes and ketones

An organic reduction is a reaction that adds hydrogen to a molecule. All kinds of carbonyl
compounds can be reduced, including aldehydes, ketones, carboxylic acids and esters. Note that
one hydrogen atom is delivered to the carbonyl carbon atom during ketone and aldehyde
reductions, but two hydrogens become bonded to the former carbonyl carbon during carboxylic
acid and ester reductions.

6. Reduction of carboxylic acids

LiAlH4 is a stronger reducing agent for the reduction of carboxylic acid and esters. NaBH 4 cannot
reduce these two.

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Note: LiAlH4 as a selective reducing agent, can reduce the carbonyl group but not the Carbon-carbon
double bond. Hydrogen with metal catalyst will reduce both the carbonyl group and the carbon-carbon
double bond. NaBH4 works like LIAlH4, but is a weak reducing agent and can reduce aldehydes and
ketones only –is not strong enough to reduce COOH or esters.
Practice Questions
1. (i) Which carbonyl compounds would you reduce to obtain the following alcohols?

(ii) Identify each alcohol as primary, secondary or tertiary.

Solution:
 A primary alcohol can be prepared by reduction of an aldehyde, an ester or a carboxylic
acid.
 A secondary alcohol can be prepared by reduction of a ketone.
 A tertiary alcohol can’t be prepared by reduction.
(a) The target molecule is a secondary alcohol, which can only be prepared by reduction
of a ketone. Either NaBH4 or LiAlH4 can be used.

(b) The target molecule is a primary alcohol, which can be prepared by reduction of an
aldehyde, an ester or carboxylic acid reductions.

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 2. Which reagent would you use to accomplish each of the following reactions?

3. What carbonyl compounds give the following alcohols on reduction with LiAlH4?

Reactions of alcohols
 Reactions of alcohols involve breaking either of two bonds: C—OH bond, removal of OH or the
O—H bond, removal of H.
 Either removal involves substitution of OH or H with another group, or elimination, in which
case an alkene is formed.

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a) Basic properties
R—O—H
If bond breakage is here it exhibits basic properties.
i. Reaction with hydrogen halides
ROH + HX → R—X + H2O
Reactivity of HX: HI > HBr > HCl
Reactivity of ROH: 3o > 2o > 1o .
e.g.

ii. Dehydration of alcohols to yield alkenes

One of the most valuable C-O bond reactions of alcohol is dehydration to give alkenes.
The C-O bond and a neighboring C-H are broken, and an alkene π bond is formed.

iii. Reaction with phosphorus trihalide

3R-OH + PX3 → 3R-X + H3PO3
(PX3= PCl3, PBr3, PI3)
b) Acidic properties –Reaction as acids
R-O-H --Cleavage at the bond between O and H.
e.g. Reaction with reactive metals
2RO-H + 2M → 2RO-M + H2(g) (M=Na, K, Li, Mg, etc)
e.g. 2CH3CH2OH + 2Na → 2CH3CH2ONa + H2(g)

c) Ester formation
ROH react with carboxylic acids to form an ester, a sweet smelling substance. An acid
catalyzed reaction.

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 d) Ether formation
When two, similar or different, alcohol molecules combine, giving off a molecule of water, an
ether is formed. Because the reaction releases water, it is catalyzed by a dehydrating agent (conc.
H2SO4).

e) Oxidation
 Oxidation of alcohols involves the loss of one or more hydrogens from the carbon
bearing the –OH group. The product formed depends on whether the alcohol is primary
(1o), secondary (1o) or tertiary(1o).
 Tertiary alcohols are resistant to oxidation.
 Secondary alcohols are oxidized to ketones.
 Primary alcohols are oxidized to aldehydes or carboxylic acids, depending on what
oxidizing agent is used.
 Common oxidizing agents are:
 Acidified KMnO4 or K2Cr2O7: These are strong oxidizing agents and oxidise
primary alcohols straight to carboxylic acids. The aldehyde formed is short-lived
and so rapidly converted to carboxylic acids.
 Pyridinium chlorochromate (PCC): A mild oxidizing agent. Oxidises a
primary alcohol to an aldehyde only, –not able to oxidise it further. Also oxidises
secondary alcohols to ketones.

Mechanisms
Reaction of alcohols with HX and Dehydration of alcohols to alkenes.
1. Reaction of alcohols with hydrogen halides
(CH3)3COH + HCl → (CH3)3CCl + H2O

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 NB: All other alcohols react with HX in the same way and all have the same mechanism.

2. Dehydration of alcohols to give alkenes

Dehydration requires an acidic catalyst to protonate the hydroxyl group of the alcohol and convert
it into a good leaving group. Loss of water, followed by loss of a proton, gives an alkene.

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 Note: To drive the equation to the right water has to be removed, hence the use of dehydrating
agent, conc. H2SO4.
Revision exercise
1. Write chemical equations for the reactions that take place between each of the following pairs of
reagents.
a. 2-Butanol and hydrogen bromide
b. 3-Ethyl-3-pentanol and hydrogen chloride
c. Propan-1-ol and phosphorus trichloride

Phenol
Phenols are compounds that have hydroxyl groups bonded to aromatic rings.

The word phenol is used both as the name of a specific substance (hydroxybenzene) and
as the family name for hydroxy-substituted aromatic compounds. Phenol is used as the
parent name rather than -benzene.
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Examples of naturally occurring alcohols and phenols
1. Menthol: This is a naturally occurring terpene alcohol, obtained from peppermint or
other mint oils. It is used as topical anesthesia and for relieving minor pain e.g.
muscle strain.

2. Phenol is widely found in nature. Methyl salicylate is a flavoring agent found in oil of
wintergreen.
Analysis for alcohols
1. Reaction with carboxylic acids in the presence of an organic acid
 When mixed with –COOH in the presence of an organic acid, a sweet smelling substance
(an ester) is formed.
2. 2o and 1o alcohols decolorize acidified KMnO4 and turn orange K2Cr2O7 green.
3o alcohols do not give a positive test.
3. Lucas test (Lucas reagent is a mixture of conc. HCl and ZnCl2)
 This distinguishes whether an alcohol is 1o, 2o, or 3o.
 They all form an insoluble chloride.
 Formation of a chloride is indicated by the cloudiness that appears when the insoluble
separates from solution; hence, the time required for the cloudiness to appear is a
measure of the reactivity of the alcohol.
 3o reacts immediately with Lucas reagent.
 2o reacts within 5 minutes.
 1o does not react appreciably at room temperature.

Uses of alcohols
Learners to do as an assignment
Polyhydroxy alcohols:

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These are compounds that possess 2 or more hydroxyl group. They provide more than one site per
molecule for hydrogen bonding, and will have a much higher boiling point than the monohydroxy of the
same number of carbon atoms.

Glycols
Also called diols. These are alcohols with two –OH groups. They are named like other alcohols except
that the suffix diol is used and 2 numbers are needed to tell where the two hydroxyl groups are located.
e.g. Ethan-1,2-diol.
Glycerol
Glycerol is a constituent of fat. CH2OHCH2OHCH2OH
Fatty Acids
These are carboxylic acids with long, unbranched carbon chains. They are called fatty acids because they
are liberated from fats and oils by a hydrolysis process (saponification). Some contain C-C double bonds.
Examples:

Fats: A fat is an ester derived from a molecule of glycerol and three molecules of fatty acids.

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  The fatty acid used in fat may be the same or different. They may also contain unsaturation in the
form of one or more cis double bonds.
 Fats with no C-C double bonds, termed as saturated fats, are typically solids, and are of animal
origin. Fats containing double bonds, termed as unsaturated fats, are oily liquids. Olive oil, a
plant product, is an example of an unsaturated fat.
Uses of fats: Fats, which are stored in a highly concentrated form in the body, serve as the
biological store house of energy reserves.
ETHERS
 These are compounds having two alkyl groups joined together by oxygen.
 Their general formula is R1-O-R (R1 and R are alkyl groups, either same or different).
 Like alcohols, ethers are polar as compared to the hydrocarbons, which are non-polar.
 Ether names are derived from the names of the alkyl groups and the word ‘ether’.
 Diethyl ether is a common ether used as an anaesthesia.
 Examples of ethers and names:
CH3-O-CH2CH3 Ethyl methyl ether
CH3CH2CH2-O-CH2CH3 Ethyl propyl ether
CH3CH2-O-CH2CH3 Diethyl ether
CH3-O-CH3 Dimethyl ether
Physical properties
Boiling point
 The C-O-C possess some slight polarity and this affects the BP of ethers which have comparable
molecular weights with alkanes, but lower than those of alcohols.
 The hydrogen bonding that holds alcohol molecules strongly together is not possible for ethers,
since they contain hydrogen bonded only to carbon.
Solubility in water:
 The solubility of alcohols is attributed to hydrogen bonding between water molecules and alcohol
molecules. The water solubility of ethers arises in the same way. Through the unshared electron
pairs on oxygen, ethers can accept hydrogen bonds provided by water.

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Questions
1. Ether molecules do not exhibit H-bonding. Explain.
2. Ethers dissolve in water. Explain.
Preparation of ethers
a) Dehydration
 Are prepared by reactions of the corresponding alcohols with sulphuric acid. Since a
molecule of water is lost for every pair of alcohols, the reaction is a kind of dehydration.

Note: Heat an alcohol with conc H2SO4 at about 180oC gives an alkene.
 A combination of two different alcohols usually yields a mixture of three ethers
e.g.

b) Williamson synthesis
RX + R’ONa → R-O-R + NaX
e.g.
CH3Br + CH3CH2CH2CH2ONa → CH3CH2CH2CH2OCH3 + NaBr
Butyl methyl ether
Reactions of ethers
They undergo only one kind of reactions, cleavage by acids (conc. HX)
R1-O-R + 2HX → R1X + RX
The ether linkage is stable towards bases, oxidizing agents and reducing agents.
Revision Question
Give the structure(s) and name(s) of the following:

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Uses of ethers
1. Used as anaesthesia in surgery—induses sedation.
2. Used as a solvent in industries—dissolves both polar and non-polar organic matter.
3. Used in column chromatography to separate organic compounds.
4. Used in the preparation of Grignard reagents, especially diethyl ether.
Uses of alcohols
1.

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